Lubricating composition



Patented Feb. 26, 1946- 2,395,457 FlCE 2,395,451 LUBRICATING COMPOSITION Gordon 1). Byrkit, Niagara. Falls, N.-Y., assignor,

by mesne assignments, to The Lubri-Zol Development Corporation, Cleveland, Ohio, a corr poration of Delaware No Drawing. Application May 28, 1942,

, Serial No. 444,911

13 Claims. My invention relates to an addition agent for lubricating oils and to an improved lubricating oil formed therefrom.

This application is a continuation in part of my copending application, Serial No. 226,966, filed August 26, 1938, now Patent No. 2,309,336 dated Jan. 26, 1943, which in turn was a continuagizgin in part of Serial No. 87,464, filed June 26,

Present-day mechanical devices require lubricating oils of high film strength, It has been found that the highest quality straight hydrocarbon lubricants have a film strength insufficient for efiicient use in present-day mechanical devices. High quality straight hydrocarbon lubricants used under conditions of high pressure, low

speed and/or high temperatures, have a tendency to break down due to their low film strength, With high pressures between the rubbingsurfaces, the body of the lubricant is squeezed out and only a thin film remains. It is readil seen that with a low film strength lubricant, there is a tendency for the lubricant to break down, decompose, and allow the rubbing surfaces to come in contact and cause seizure.

It is well known that mineral lubricating oils are deficient in oiliness, which is the most important character of the lubricant when used under conditions of boundary lubrication where the viscosity of the lubricant plays little or no part. Boundary lubrication conditions are obtained when engines are operating at heavy loads, low speed, or if for any reason the supply of lubricant is cut off or not sufiicient. This last condition may exist when for mechanical reasons the lubricant pump is not functioning properly or when the-lubricant feed line is clogged with I foreign matter.

In starting idle mechanical equipment which islubricated from a sump by pumping or circulating the lubricant, there is always a short pe of time in which the rubbing surfaces must operate under conditions of dry friction if ordinary hydrocarbon lubricants are used, With dry friction the wear on friction surfaces is extreme; and during cold weather when the lubricant is slugglsh or during periods when the lubricating system is not functioning properly for one reason or another, rubbing surfaces may not only suffer considerable wear but may be damaged to the I point where they must be replaced. By means of m invention, it is possible to produce a material which when blended with hydrocarbon lubricants has the very important property of reacting with the metal surfaces, .Denetrating and/or adsorbing on the metal, leaving a film of lubricant with high oiliness characteristics, which remains on the metal surface irrespective of the length of time the machine has been idle. This high oiliness film gives very smooth operation, which may be easily discerned by the experienced operator and lubricating engineer.

One object of my invention is to provide materials which when added to mineral lubricating oils improve their oiliness and load-carrying ability and enable the oil to lower the friction be. tween the rubbing surfaces.

Another object of my invention is to provide a material which when blended with the hydrocarbon oils will produce a lubricant which will maintain a very low coefii'cient of friction when diluted with light hydrocarbons such as are obtained in an automobile crankcase by incomplete combustion of the fuel.

A further object of my invention is to provide a material which when blended with hydrocarbon lubricants will confer upon it penetrative lubricity characteristics. It has been found that by my process a lubricant is produced which does not drain off the rubbing surfaces when idle, thereby providing a lubricating film on the rubbing surfaces at all times and being of great value to the life of the machine. in cold-weather starting when the lubricant is very stifl and sluggish.

A still further object of my invention is to provide a material which when blended with a lubri cant enables it to produce a more nearly constant coeflicient of friction, thereby insuring smoother engine operation. r It is well known to the art that the additio of certain chlorinated or otherwise halogenated organic materials to mineral lubricants improves the character of the latter in these various respects. For example, U. S. Patent 1,944,941, issued to Bert H. Lincoln and Alfred Henriksen on January 30, 1934, describes a lubricating oil comprising in combination a hydrocarbon oil and a small quantity of certain halogenated esters, which improve the oiliness and load-carrying ability of the mineral oil, confer upon it penetrative lubricity characteristics and enable it to reduce the coeflicient of friction between rubbing surfaces.

I have found that material excellently suited for the purpose of improving these characteristics of hydrocarbon oil is the v halogen-bearing material which may be obtained by the interaction of various halogenated materials with salts of organic acids. The halogenated organic materials are preferably selected from those which contain one or more long chain hydrocarbon radicals; such radicals desirably having at least ten carbon .atoms. The organic acid salts referred to above will usually be metallic salts and of these the alkali metal salts such as those of sodium and potassium arepreferred. Salts of other metals, such as those of the alkaline earth metals may also be used. The salts used will also decause of residual halogen introduced with the halogenated material and not removed by the I reaction with the anhydrous metal salt, and/or because the particular anhydrous metal'salt selected to be reacted with the organic acid contains halogen and/or because halogen is introduced into the product in a separate and distinct halogenation reaction subsequent to the forma tion of the product. a

. These halogen-bearing products are preferred to the halogen-free products because of superior lubricating characteristics which the former confer upon the lubricants containing such products including higher film strength, resistance to the formation of harmful deposits and sludge, and the like.

The properties of the esters contemplated hereby for use as addition agents in lubricants which render them particularly suitable-for this use as compared with esters generally are-their complexity and their compatibility with lubricating oils. The complexity results from the nature of their preparation since the halogen-containing constituent of the condensation reaction may I have the halogen attached to the organic material at a variety of points, or it may result from the halogenation process which may follow the condensation reaction. In either case, the range of products resulting is such that all of the molecular structures produced are suitable for this use rather than being of such widely different character as to include substances which would be ated by direct treatment with the halogen at ordinary or elevated temperatures.

In the prior art, references are made to mono- -chlom paraffin, dichloro paraflin, trichloro paramn and the like as if these products were the result of direct chlorination of paraffins to the desired chlorinated product. I have found these materials are crude mixtures of chlorinated hydrocarbons and invariably contain unchlorinated hydrocarbons, monochlorinated hydrocarbons, dichlorinated hydrocarbons, and polychloro hydrocarbon derivatives. For example, a so-called "trichloro parafiln wax containing 24 per cent chlorine, which corresponds closely to the percentage of chlorine in the trichloro compound, was separated by means of crystallization from acetone. The least soluble portion consisted of unchlorinated wax. The next least soluble portion consisted of a mixture of monochloro wax and unchlorinated wax. The percentage of un-- priate amount of halogen, speciflcallychlorine,

pure halogenated wax. Even though the approis introduced into a wax to form a monochloro wax, the crude chlorination mixture will contain,

in addition to small amounts of chlorine and hydrogen chloride and the desired monochlor wax, unchlorinated wax and more highly chlopoly-chlor waxes begins when only per cent by weight of chlorine has been introduced into the paraffin hydrocarbon. This formation of diand higher poly-chlor waxes proceeds more rapidly than the chlorination of the hydrocarbon to the.

monochlor compound so that the proportion of the latter in a crude chlorinated mixture decreases rapidly and is at a maximum when about 10 per cent of chlorine has been introduced. At

this point, a typical chlorinated mixture will contain about 25-30 per cent of unchlorinated wax, 40-50 per cent of monochlor wax, and about 20-25 per cent of dichlor wax, as well as higher chlorinated waxes. Even when as much as 24 per cent by weight of chlorine is introduced into a paraffin wax, about 10 per cent of unchlorinated hydrocarbon is still present in the mixture.

The removal of unchlorinated hydrocarbons from the crude chlorinated mixture is the first step in preparing relatively pure mono-halogen compounds and higher halogenated compounds, but it will be obvious that the chlorine compounds, when separated from the unchlorinated hydrocarbon, form a crude mixture of hydrocarbons in various stages of chlorination. The other acts. It is impossible to directly obtain any relatively pure homogeneously halogenated wax by merely halogenating wax. To obtain the halogenated wax, which is an essential component of chlorinated wax in the original mixture was found to be 7.2 per cent. Thus, even in a trichloro paraffin" so-called of the prior art, there is a large percentage of unchlorinated wax'and quantities of monochlorinated wax and dichlorinated wax, besides trichlor wax and more'highly chlorinated waxes. i

In carryingout the method of my invention, the use of a crude mixture of halogenated waxes will not give the same results asa substantially chlorine as the monochlor product.

this invention, a special processing step must be employed.

The halog'enation of most petroleum hydrocarbons lowers their melting points; and, to a cer-v tai'n degree, the greater the extent of halogenation, that is, the more halogen atoms per molecule, the lower the melting point. The decrease in melting point is stepwise. This permits me to separate halogenated hydrocarbons from the monohalo hydrocarbons, the monohalo hydrocarbons from the dihalo hydrocarbons, and the dihalo hydrocarbons from th trihalo hydrocarbons.

Having selected the hydrocarbon in accordance with the desired final product, I halogenate the hydrocarbons until approximately that amount.

of halogen is absorbed which will produce monohalo compounds, if these are desired, or larger amounts of halogen to produce di-, and higher poly-halo hydrocarbons when these products are desired. For example, in the' manufacture of a vary from not les than 8 to not more than 12 per cent without being disadvantageous. The percentage of chlorine introduced into the hydrocarbon will be less' in the case of the higher molecular weight, higher melting hydrocarbons. The chlorination may be accomplished by any suitable method and any appropriate apparatus.

Thi may I prefer to melt the wax and agitate thoroughly while the chlorine gas is'introduced into contact therewith so as to be well distributed through the liquid. The heat of reaction is ordinarily ample to maintain themixture in the liquid state without further heating. I make provision for the escape of quantities of hydrogen chloride gas which are evolved and for unreacted chlorine. When a sufficient quantity of chlorine has been introduced, I blow the mixture with air or other inert gas such as carbon dioxide until the hydrogen chloride and free chlorine are substantially removed.

Even though the appropriate amount of chlorine is introduced into the wax to form a monochlor wax, as I have pointed out above, it will be found that the crude chlorination mixture con ,tains in addition to the by-product hydrogen chloride and the desired monochlor wax, also unchlorinated wax and more highly chlorinated waxes.

The unchlorinated wax is separated from the air-blown 'mixture by pressing at such temperature that the chlorinated waxes are largely liquid and the unchlorinated wax is mostly solid. The appropriate temperature to -which the mixture must be chilled before the pressing operation begins will depend upon the character of the hydrocarbon used initially and may vary con siderably. For example, when a wax having a melting point of 120 F. is used as the starting material, a temperature of about 80-90 F. is suitable for the separation of unchlorinated wax from the mixture.

Other separation processes, for example, sweating, may be employed to separate the solid, halo- ,genated wax from the liquid halogenated waxes.

The liquid halogenated waxes will consist largelyof monohalo wax and dihalo wax. These may be separated by crystallization from acetone or any other suitable solid, using a solvent-chlor wax ratio of from 1 to 1 to 20 to 1. The solution is prepared by warming and is then chilled to approximately 15" to 20 F. 'to precipitate the halogenated waxes which are then removed by filtering, pressing, settling, or in any other suitable manner.

The monohalo wax is precipitated out of the solution nearly quantitatively, and its separation from the dihalo and polyhalo waxes present-is readily accomplished.

Instead of acetone, such selective solvents as methyl-ethyl ketone, acetone-benzene mixtures.

acetone-methylene chloride mixtures, 01 various halogenated solvents may be employed. It will be obvious that the quantity of solvent and the temperature to which the solution should be chilled will depend upon the particular materials being processed and may be readily determined empirically, The halogenated solvents serve to aid in the precipitation of unhalogenated waxes while benzene increases the solubility of the more highly halogenated materials.

The aboveseparation by means of solvents and chilling was carried out on several samples which had been chlorinated to the theoretical monochloro stage. The monochlor wax thus obtained was found tocontain approximately the theoretical chlorine content. Various. batches show chlorine contents of 10.1, 10.5, 10.3, and 10.8 per cent. The theoretical chlorine content is 10.2 per cent so that it will be apparent that the monochlor wax obtained is substantially free from unchlorinated waxes and highly chlorinated waxes. Th monochlor wax was found to behave very much like a pure compound. I proved the homogeneity of my monochlor wax. for example, by chilling until approximately half of the material had solidified. Solid and liquid portions were separated by filtration and contained 12.1 and 11.4 per cent chlorine respectively. My monochlor wax is therefore free from both unchlorinated wax and more highly chlorinated .wax. Similarly, I may prepare according to my invention diand poly-chloro waxes free from unchlorinated wax and monochlor wax as well as mor highly chlorinated waxes.

Any of the relatively pure halogenated waxes may be used in carrying out my invention. A selected one of these waxes is condensed with the anhydrous metal salt of an organic acid in producinga product, which may be used either directly or after halogenation as the addition agent of the compounded lubricants of my invention;

The organic acid may be of any type, that is. aliphatic, aromatic, or heterogeneous, and may belong to more than one of these classes.

various organic acids which may thus be employed:

(a) Fatty acids such as the following:

Acetic acid Chlor acetic acid Propionic acid Chlor propionic acid Butyric acid Oxalic acid Lactic acid Succinic acid Tartaric acid Stearic acid Palmitic acid Laurie acid Dichlorstearic acid Oleic acid Ricinoleic acid Cycloaliphatic acids, such as:

Napthenic acids Hexahydrobenzoic acid Alkylated hexahydrobenzoic acids Lauryl hexahydrobenzoic acid. Cetyl hexahydrobenzoic acids Hexahydrosalicylic acid Hexahydrophthalic acid Alkylated hexahydro-phthalic acids Lauryl hexahydro-phthalic acids Dilauryl hexahydro-phthalic acids Cetyl hexahydro-phthalic acids Dicetyl hexahydro-phthalic acids Aromatic substituted fatty acids, such as:

Phenyl acetic acids Phenyl propionic acids Phenyl stearic acid Chlorphenyl stearic acid Tolyl stearic acid Xylyl stearic acid Xenylstearic acid Naphthyl stearic acid Phenoxy phenyl stearic acid Benzoyl phenyl stearic acid Hydroxy phenyl stearic acid Chlor phenyl stearic acids Phenyl palmitic acid Aromatic acids Benzoic acid Monochlor benzoic acids Dichlor benzoic acids Salicylic acid The following table gives representative examples of- In the foregoing table it will be observed that I have indicated that the halogen or more speciflcally chlorine bearing derivatives of certain of the named acids may be'employed, and in this connection, it should be noted that any of the named acids may be halogenated and used as one 01' the reagents in the preparation of addition agents which are particularly eillcient in improving the characteristicsof mineral lubricating 'oil when blended with them. The halogenated acid will be selected as one of the starting materials when, as hereinafter pointed out for example, it is desired that the halogen in the end product be in the acid radicle.

The chosen organic acid is converted to the sodium or other metallic salt by means of neutralization with asuitable base, such as sodium The condensation products are, of several types depending on the structure of the starting materials:

I. Esters from monohalogen compounds: A. Esters from monohalogenated hydrocarbons.

The monohalogenated hydrocarbons which may be used with a selected anhydrous metal salt of an organic acid in producing this type of ester are represented by the following:

l. Monochloroparaifin wax 2. Monochloro-decane 3. Monochloro-pentane 4. Monochloro-gasoline hydrocarbons 5. Monochloro-kerosene hydrocarbons These end-products are esters of the type RCO R derived from the metal salt, RCOQM and the halogenated hydrocarbon, RX, where M represents a metal; X represents a halogen. These esters hydrolyze to form an acid and an alcohol. B. Di-esters from mono-halogenated esters.

These are of three types depending on the position of the halogen.

1. Halogen in the acid radical.

These esters are of the type, RCH (O-CO-R') (CH1).C0,R, derived from the metal salt R'OOOM and the monoehloro-ester, RCHGI(CH1),.CO,R B may be H or an organic radical; n may be zero or any integer. These esters are disting'uished in that they hydrolyze to form analcohol, R0H, an acid, RCO H, and a hydroxy acid, RCHOH(CH 00 B. Examples of mono-halogenated esters which may be used are: a. Octadecyl alpha-bromostearate b. Monochloro-carnauba wax c. Monochloro-beeswax 4 2. Halogen in the alcohol radical. V

- These esters are of the type, BCOIR'O- (JO-R", derived from the metal salt R"C 0 M and .the monochloro-ester, RCO RX in which R is a divalent or- 02H and glycol, R(0H), which may be vicmal or disjoined depending on the position of the halogen. Examples of mono-halogenated esters which may be used are:

a. Beta-chloroethyl stearate b. Monochloro-octadecyl stearate c. Monobromocarnauba wax esters except that the p 3. Halogen in both the acid and alcohol radicals.

These esters may be derived by means of condensation reactions'in which both the reagents are. halogen-containing and wherein the condensation reaction is carried out so as to leave residual halogen on the long chain aliphatic material such as parailin wax.

H. Esters irom di-halogen compounds A. Esters from di-halogenated hydrocarbons 1.. When both halogen atoms are involved in the reaction: These esters are of the type, (RCOz)2R, in which RG01 is the radical derived from the metal salt, RCO M, and R is a divalent organic radical derived from the dl-halogcnated hydrocarbon, RClz. These esters are distinguished in that they hydrolyze to form an acid, RCOzH, and a ketone if both halogen atoms in RCh are on the same carbon atom; an acid and a vicinal glycol if the halogens are on adjoining carbon atoms; and an acid and a dis oined glycol if the halogens are on disjoined carbon atoms.

Examples of di-halogenated hydrocarbons which may be used are:

l. 3, 3-dichlorodecane 2. 2, S-dichlorodecane 3. 1, 10,dichlorodccane 4. Dlchloroparafiin wax 5. Dibromo-gasoline hydrocarbons 6. Dichloro-kerosene hydrocarbons 2. When only one halogen atom is involved in the reaction and the second halogen atom remains in the product, the esters are of the type, RCOnRCl. These esters will hydrolize to form an arid RCOzH and a halogen-containing co B. Esters from di-halogenated esters :{Vhen both halogen atoms are involved in the reac ion:

These are of three classes containing several types depending on the position of the halogen atoms.

1. Both halogens'in the alcohol radical These esters are of the type, RCOzR" (O-CO-R), in which R is a trivalent organic radical. The esters are derived from the diehloro-esters RCOzR'C-lz. These esters are distinguished in that they hydrolyze to form two ends, RO0 H and R"OO H, and a trihydroxy organic compound R(OH)1 or a hydroxyketone. Examples of dihalogenated esters which may be used are:

a. 2.2-dichloroethyl stearate b. Dichloro-carnauha wax c. Dichloro-candelilla wax 2. Both halogens in the acid radical These esters are -of the type, (E00,),- RQO R", in which R is a trivalent organic radical. The dichloroesters from which these are derived have the formula R'ClrCOgR". These esters are distinguished in thatthey hydrolyze to form an alcohol,

R0H, an acid, RCO2H, and a dihydroxyacid R(OH,C0:H or a keto-acid if both halogens were originally on the same carbon atom. Examples of dihalogenated esters which may be used are:

a. Methyl alpha, alpha-diehlorostearate b. Dichloro-beeswax c. Dibromo spermaceti d. Methyl alpha, beta-dichlorostearate c. Ethyl cinnamate dihromide 1'. Methyl alpha, iota-dichlorostearate 3. One halogen in each radical These esters are of the type,

II RCO zR'C OzR-"O GR in which R and R are divalent organic radicals. The starting chl have the formula RCl C'O RK'Cl. Those esters are distinguished in that they hydrolyze to form. an acid. R z a hydroxyacld, R'(OH)C0,H, and a glycol, R"(0l1)| which may be vicinal or disjoined depending on the position of the original halogen atoms. Ex-

amples of iii-halogenated esters which may be are. a. Beta-chloroethyl alpha chlorostcarate b. Gamma-ohloropropyl, iota-chlorostearc. Dichloro-candelilla war Where only one halogen atom is involved in the reaction the prod ucts will be of the same me as those derived from momrhalnzenat uct will contain one atom oflnlogen, e. g.

noom'oom'm or RGOzR'ClCOzR" -III. Estersfrom poly-halogen compounds.

The products of our invention may derive their halogen content from a'plurality of sources, that is. fromeither or. both of the starting materials, or by direct halogenation of the reaction product.

The halogen 'oompoimd may, during the condensation reaction, lose all or only p rt of its halogen. Furthermore, the acid whose sodium or other metal salt is used in the condensation re used in hypoid gears and in crankcases of internal combustion engines. The residual halogen in-- creases the polarity of the-molecule which has an improving effect upon the oil in which it is blended. In order to obtain substantially halogen-free esters as final products which are then subsequently halogenated before use. I treat my halogen compound at a sumc'iently high temperature for a suiiicient time with a suitable excess of a halogen-free sodium salt as described below.

For use in lubricating oils, it is desirable that the compounds employed should have a vapor pressure of less than atmospheric at a temperature of about 250 F. Compounds having this vapor pressure will not vaporize during use in an internal combustion engine or as a crankcase lubricant. v

The condensation of the chlorinated wax with the anhydrous salt, for example, the anhydrous sodium salt, is preferably elfected by heating these two components in the presence of small amounts of an acid anhydride and a tertiary base, such as pyridine or dimethylaniline. If the organic acid used is cheaply available in the form of the anhydride, that anhydride is preferably used as a condensing agent: thus; for example, if acetic acid is used to prepare the anhydrous sodium salt, then acetic anhydride is preferably used asthe with water and drying the same by suitable means, such as for example, blowing with air at an elevated temperature.

The addition agent may be used-in a wide range of concentrations in the mineral oil base, the properties of which are to be improved. Generally, amounts on the order of .25%'to 5% will besuitable for most uses, although amounts from aboutv .1% to about will be found to have general'utilitv.

Where extreme conditions are to be encountered, the addition agent. may be utilized in amounts from an eifective amount up to about 20%. The term "'eflective amount" is used to denote that amount of the particular addition agent necessary in order to show a substantial increase in'the extreme pressure properties of the mineral oil base to which the same is added.

Various types of lubricants are susceptible to treatment by this invention, including paraflin base, naphthenic base and/or asphaltic base hydrocarbon oils, and other oils of lubricating viscosity, such as animal and vegetable oils, namely, castor oil, sperm oil,.eottonseed oil, lard oil, corn oil, and synthetic oils, including hydrogenated oils on the type of service for which the lubricant is designed. In general, a compounded lubricant made in accordance with my invention should have a viscosity for a particular use which is the sameas that viscosity of a plain mineral luhri condensing anhydride; however acetic or any.

other cheaply available acid anhydride is suitable to effect the condensation.

The use of a tertiary base such as pyridine or dimethylaniline serves toincrease the rate of reaction between the components so as to efi'ect the condensation in a shorter time. In general, the

condensation is efi'ected by heating the components to a temperature of from 100 to 200 degrees 6., usually about 140 degrees C. for 8 to 16 hours;

however in the presence of the tertiary base, condensation is completed in a much shorter time; namely, from 4 to 8 hours at this temperature. Thetime and temperature conditions given above will be a sufilciently definite indication to those skilled in the art to carry out the condensation reaction involving the several named com-- ponents. The time and temperature conditions siven above as an illustration may be varied when using different reagents and also in accordance with the amount of residual halogen desired to be retained in the end product.

The condensation product or addition agent asthu's prepared if no residual halogen is present therein may be halogenated to any desiredextent, and for certain purposes a product thus mnaredls preferable to that resulting from a condensation reaction carried on under such conditions that a certain amount of residual halogen In whatever way the addition agent is prepared.

it will desirably berefinedbefore use'bywashing cating oil used for the same purpose. For example, for most internal combustion engines of the usual automotive type, the viscosity will be within the S. A. E. 10, S. A. E. 20 and S. A. E. 30 ranges: while for heavy-duty and aviation'engines higher viscosity ranges are sometimes used, for example the S. A. E. 40 andS. A. E. 50 ranges. Since the compositions of this invention are-suitable for restricted'range of from about to about I40 being most generally used.

The highly refined mineral lubricating oils suitable for use as the base in the improvedcompositions of my invention may be conveniently classified in accordance with theirviscosity index, three-such classes being oils having a V. I. up to 30; oils having a V. I. from 30 to about 70; and

oils having aV. I. of above 70 Obviouslythe oil base selected may contain appropriate constituents in addition to plain mineral oil such as pour point depressors and the like, since these conventionally employed materials have been found entirely. compatible" with the addition agents which characterize the final blends com- The following example'of my invention is given to show one embodiment thereof. but it is to b j nnderstood'that my invention is not limited thereto excep'tfin so far as pointed out in the claims.

All quantities are given in parts by weight. One hundred thirty parts of a relatively pure m'ono-,

chlor wax were heated with 58 parts of the anhydrous sodium salt of chloraoetic acid and 4'! parts of free chloroacetic acid inthe presence of fiveml. oi acetic anhydride and two ml. of pyridine at to C. for 6 hours. I The rsulting condensation product was washed with water and dilute sodium carbonate solution to remove free' The viscosity of the oil base used will depend 9; Mineral the load carrying ability, oiliness and penetrative lubricity characteristics, and reduced the coemcient of irictionbetween rubbing metal surfaces.

The presence of chlorine in the condensation product was in part responsible for the extremely high increase in illm strength and the reduction in the coei'ilcient of friction.

While it is believed unnecessary to more specifically indicate particular condensation products prepared in the manner indicated above and the range of percentages within which the same may 15 of Cl from the beta-chloro-ethyl dibe used, nevertheless the following is submitted as an additional guide in the selection and mode of use of the materials comprising this invention.

Parts by weight vl. Mineral nil 99.5

I Condensation product of monochlor paraflin wax with sodium chloracetate 0.5

-2. Mineral 98 Condensation product of monochlor wax with sodium dichlorstearate- '2 3. Mineral oil 99 Condensation product or monochlor wax with sodium dichlorbenzoate 1 .4. Mineral oi I 98 Condensation product of monochlor wax with sodium chlornaphthenate 2 I5. Mineral nil 99 Condensation product of monochlor wax with sodium chlorsalicylate"; 1

6. Mineral oil 99.

Condensation product of monochlor wall with sodium chlorphenylstearatesn." 1 7.. Mineral oil 99 Condensation product of monochlor parailin wax with sodium dichlorphthalate l s. Mineral 1' 99 Condensation product oi monochlor par-- and wax with sodium salt of monomethyl ester of dichlor-phthalic acid 1 /CONa canon Condensation product 0! dichlor 'parainn wax with sodium acetate (reacted under conditions such as to remove only approximately, one atom of 'chlo rine from the dichlor wax) 1 l9. -Minel'al on 99 Condensation product. or dichloro-keroe sene hydrocarbon with sodium benzoate (reacted under conditions such as to remove only approximately one atom of Cl from the dichlor kerosene) 1 11'. Mineral Oil 99 Condensation 'product of monochlor carnauba' waxwith sodium chloracetate- 1 12. Mineral ofl 99 Condensation product oi'monochlor car- 'nauba wax with sodium chlorbenzoate 1 13. Mineral oL e 99 Condensation product of monochlor carnauba wax with sodium chlornaphthenate Condensation product of methyl dichlorchlorstearate) v 17; Mineral nil 99 Condensation productoi methyl dichlorstearate with sodium acetate (reacted 20 under conditions such as to remove only approximately one atom of chicrine from the methyl dichlorstearate) 1 l8.- Mineral stearate with sodium chloracetate l 19. Mineral oiL 99 Condensation product of methyl dichlor stearate with sodium chlorbenzoate 1 Mineral oil 99 Condensation product of monochlor parailln wax'with sodium acetate (the reaction product having been chlorinated untilit contained about 20% of 35 chlorine) 2i. Mineral oil (S. A. E. gear oil) sulphurized methyl linoleate 2 Condensation product or mono-chlor paraffin wax with odium chloracetate. '3

Inthe above examples, I have used a chlorinated material, but it is to be understood that any of the halogens are suitable in the preparation of my condensation products. For example. due- 45 rine, bromine, or iodine'may be used? but since chlorine is so cheaply available, it is the preferred embodiment of my invention. 7

It will be understood that certain features and subcombinations are of utility and may be emso pioyed without reference to other features and This is contemplated by and sub'combinations. 4 is within the scope or'my claims. It is further obvious that various changes may be made in detail within the scope of my claims without departing from the spirit of my invention. It is therefore to be understood that my invention is not to be limited to the specific details shown and described.

Other modes or applying the principle or the invention may be emlflfl ed. change being made as regards the details described. provided the teatures s'tatedin any of the following claims, or the equivalent oi such, be employed.

I therefore particularly point out and distinct- 'dl lyclaimasmyinvention: l. Aiubricatina composition comprisina a maior proportion oilubricating oil and a minor amount of a synthetic material obtained by con- 'densing a homogeneous monochloro-wax with 10 anhydrous sodium ortho-chlorobensoatein the presence of acetic anhydride and pyridine.

2. 'A lubricating composition comprising a major proportion of. lubricating oil and a minor amount of a halogen-hearing material obtained 1 -fllbycoridensingahalosenatedwaxwithananhb drous metal salt of an organic acid in the presence of an organic acid anhydride.

3. A lubricating composition comprising a major proportion of lubricating oil and a minor jor proportion of lubricating oil and aminor amount of a halogen-containing material obtained by condensing a halogenated wax with an anhydrous salt of an organic acid in the presence of an organic acid anhydride and a tertiary base.

5. A lubricating composition comprising a major proportion of lubricating oil and a minor amount of a chlorine-containing material obtained by condensing a chlorinated wax with an anhydrous salt of an organic acid in the presence of an organic acid anhydride. t 6. A lubricating composition comprising a major proportion of lubricating oil and a minor amount of a chlorine-containing material obtained by condensing a chlorinated wax with an anhydrous salt of an organic acid in the presence of an organic acid anhydride and a ter-.

, tiary base.

7. A lubricating composition comprising a major proportion of a hydrocarbon oil and a minor amount of a synthetic halogen-containing material obtained by condensing a relatively pure homogeneously halogenated wax with an anhydrous halogen-containing metal salt of an organic acid in the presence of an organic acid anhydride.

8. A lubricating composition comprising a main the presence of an organic acid anhydride and a tertiary base.

9. A lubricating composition comprising a major proportion of lubricating oil and a minor amount of a synthetic halogen-containing material obtained by condensing a relatively pure homogeneously chlorinated wax with an anhydrous salt'oi an organic acid in the presence of an organic acid anhydride.

10.. A lubricating composition comprising a major proportion of lubricating oil and a minor amount of a synthetic halogen-containing material obtained by condensing a relatively pure homogeneously halogenated wax with an anhydrous metal salt of an organic acid in the presence of an organic acid anhydride.

.11. A lubricating composition comprising a major proportion of lubricating oil and a minor ior proportion of a hydrocarbon oil and aminor 1 proportion of a" synthetic halogen-containingamount of a synthetic halogen-containing mate rial obtained by condensing a relatively pure homogeneously halogenated wax with an anhydrous metal salt of an organic acid in the presence of an organic acid anhydride and base.

12. A lubricating composition comprising a masalt of an organic acid in the presence of an organic acid anhydride and a tertiary base at a temperature from C. to 200 C. fora period of from 4 to 8 hours.

1 GORDON D6 BYRKIT.

av tertiary 

